EP3087614A1 - Semiconducteur d'oxyde de type p, composition pour la production d'un semiconducteur d'oxyde de type p, procédé de production d'un semiconducteur d'oxyde de type p, élément à semiconducteurs, élément d'affichage, dispositif d'affichage d'image et système correspondant - Google Patents
Semiconducteur d'oxyde de type p, composition pour la production d'un semiconducteur d'oxyde de type p, procédé de production d'un semiconducteur d'oxyde de type p, élément à semiconducteurs, élément d'affichage, dispositif d'affichage d'image et système correspondantInfo
- Publication number
- EP3087614A1 EP3087614A1 EP14875695.0A EP14875695A EP3087614A1 EP 3087614 A1 EP3087614 A1 EP 3087614A1 EP 14875695 A EP14875695 A EP 14875695A EP 3087614 A1 EP3087614 A1 EP 3087614A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide semiconductor
- type oxide
- semiconductor
- type
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000004519 manufacturing process Methods 0.000 title claims description 24
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- 150000004706 metal oxides Chemical class 0.000 claims abstract description 29
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- 239000002904 solvent Substances 0.000 claims description 12
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- 229910052749 magnesium Inorganic materials 0.000 claims description 10
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
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- 238000000231 atomic layer deposition Methods 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 2
- NRNCYVBFPDDJNE-UHFFFAOYSA-N pemoline Chemical compound O1C(N)=NC(=O)C1C1=CC=CC=C1 NRNCYVBFPDDJNE-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 2
- 150000003498 tellurium compounds Chemical class 0.000 description 2
- KLBIUKJOZFWCLW-UHFFFAOYSA-N thallium(iii) nitrate Chemical compound [Tl+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KLBIUKJOZFWCLW-UHFFFAOYSA-N 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 2
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- 150000003752 zinc compounds Chemical class 0.000 description 2
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- PIJBAYXHEGHMNO-UHFFFAOYSA-N 2-[tri(propan-2-yloxy)-lambda4-tellanyl]oxypropane Chemical compound CC(C)O[Te](OC(C)C)(OC(C)C)OC(C)C PIJBAYXHEGHMNO-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
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- KKLCYBZPQDOFQK-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1 KKLCYBZPQDOFQK-UHFFFAOYSA-N 0.000 description 1
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- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- CLUOTFHJTGLPSG-UHFFFAOYSA-L copper;7,7-dimethyloctanoate Chemical compound [Cu+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O CLUOTFHJTGLPSG-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
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- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DZFYOYRNBGNPJW-UHFFFAOYSA-N ethoxythallium Chemical compound [Tl+].CC[O-] DZFYOYRNBGNPJW-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- UESISTHQAYQMRA-UHFFFAOYSA-M formyloxythallium Chemical compound [Tl+].[O-]C=O UESISTHQAYQMRA-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000002798 polar solvent Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- KTZHUTMWYRHVJB-UHFFFAOYSA-K thallium(3+);trichloride Chemical compound Cl[Tl](Cl)Cl KTZHUTMWYRHVJB-UHFFFAOYSA-K 0.000 description 1
- HQOJMTATBXYHNR-UHFFFAOYSA-M thallium(I) acetate Chemical compound [Tl+].CC([O-])=O HQOJMTATBXYHNR-UHFFFAOYSA-M 0.000 description 1
- UFVDXEXHBVQKGB-UHFFFAOYSA-L thallous malonate Chemical compound [Tl+].[Tl+].[O-]C(=O)CC([O-])=O UFVDXEXHBVQKGB-UHFFFAOYSA-L 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
- G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
- G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
- G09G3/22—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources
- G09G3/30—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels
- G09G3/32—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels semiconductive, e.g. using light-emitting diodes [LED]
- G09G3/3208—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels semiconductive, e.g. using light-emitting diodes [LED] organic, e.g. using organic light-emitting diodes [OLED]
- G09G3/3225—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels semiconductive, e.g. using light-emitting diodes [LED] organic, e.g. using organic light-emitting diodes [OLED] using an active matrix
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
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- H01L29/772—Field effect transistors
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- H01L29/78693—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate the semiconducting oxide being amorphous
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
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- G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
- G09G3/34—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source
- G09G3/3433—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using light modulating elements actuated by an electric field and being other than liquid crystal devices and electrochromic devices
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- G09G3/34—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source
- G09G3/3433—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using light modulating elements actuated by an electric field and being other than liquid crystal devices and electrochromic devices
- G09G3/348—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using light modulating elements actuated by an electric field and being other than liquid crystal devices and electrochromic devices based on the deformation of a fluid drop, e.g. electrowetting
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- G09G3/34—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source
- G09G3/36—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using liquid crystals
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- G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
- G09G3/34—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source
- G09G3/38—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using electrochromic devices
Definitions
- P-TYPE OXIDE SEMICONDUCTOR COMPOSITION FOR PRODUCING P-TYPE OXIDE SEMICONDUCTOR, METHOD FOR PRODUCING P TYPE OXIDE SEMICONDUCTOR,
- the present invention relates to a p -type oxide
- semiconductor a semiconductor element, a display element, an image display device, and a system.
- a-IGZO InGaZnO4
- TFT thin film transistor
- a diode, an optical sensor, a solar cell, LED, or a bipolar transistor can be realized by forming a p -n junction by combining the p -type oxide semiconductor and the n-type oxide semiconductor.
- a band-gap of the oxide semiconductos can be widen, and therefore it is possible to make these devices transparent.
- a 2T1C circuit as illustrated in FIG. 7 is used as a basic driving circuit.
- so-called source follower connection is established, if the driving transistor 20 is n-type.
- a time-dependent change (especially voltage rise) of organic EL device properties causes an operating point of the driving transistor to move to another operating point at different gate voltage, which shortens a half- life of the display. This problem will not be caused if a p-type transistor is used in a driving transistor.
- the organic EL is driven by electric currents, a dispersion of current values leads to unevenness of display. Therefore, in the case where the threshold voltage of the transistor is dispersed, or changes over time, it is necessary to compensate to thereby prevent a display failure.
- the circuit becomes complicated, if it is composed only of an n-type transistor. A simpler circuit structure can be achieved by using both an n-type transistor and a p-type transistor.
- An active layer of a p-type oxide TFT is limited to an active layer containing monovalent copper (Cu), and an active layer containing divalent tin (Sn) .
- a CU2O crystal which is a monovalent copper oxide, has a dumbbell structure of O-Cu-O as a basic structure, and forms a valence band peak with a hybrid orbital between a 3d orbital of Cu and a 2p orbital of oxygen. Holes are introduced into the valence band by oxygen excess nonstoichiometry, to thereby realize p-type conduction.
- a delafossite-type crystal which is a monovalent copper oxide
- the oxide has high crystallinity and a single phase of the oxide containing Cu + .
- NPL 1 and NPL 2 each disclose a TFT using a Cu 2 0 crystal as an active layer. Since properties of the active layer cannot be controlled sufficiently, a mobility of the TFT and an on-off ratio thereof have not reached to a level suitable for practical use.
- PTL 1 discloses a TFT using a p-type material of a delafossite crystal containing monovalent Cu or Ag in an active layer. However, information, such as properties of the material of the active layer, formation method thereof, and properties of the transistor, is not disclosed sufficiently.
- tin oxide when Sn is a divalent state, i.e. , SnO.
- SnO a divalent state
- tin oxide tends to be n-type Sn02, as Sn is more stable in a state of Sn 4+ where two 5p electrons and two 5s electrons are lost, than a state of Sn 2+ where two 5p electron in the outermost shell are lost.
- tin oxide is used for a p-type active layer, therefore, it is a challenge to realize a Sn 2+ state, and stably maintaining this state.
- PTL 2 discloses a p-type TFT using SnO as an active layer.
- PTL 3 discloses, as a p-type semiconductor, an oxide containing at least two selected from the group consisting of Ag (ionic valency- l), Cu (ionic valency- ' l), Au (ionic valency: l) , Tl (ionic valency * - l), Pb (ionic valency " 2), Bi (ionic valency ' 3), In (ionic valency " l), Sn (ionic valency ' 2), and Sb (ionic valency' 3). It is necessary to dope with holes to realize p-type conductivity, but there is no description regarding hole doping of an oxide containing Tl (ionic valency ' 1), and therefore p -type conductivity has not been realized.
- NPL 1 ⁇ ' E Thin-film transistors based on p-type CU2O thin films produced at room temperature, Applied Physics Letters, VOL. 96, 2010, pp. 192102
- an object of the present invention is to provide a p-type oxide semiconductor, which has conductivity properties usable as an active layer of a semiconductor element.
- the p-type oxide semiconductor of the present invention contains ' - a metal oxide containing thallium (Tl), where the metal oxide has been hole doped.
- the present invention can solve the aforementioned various problems in the art, and can provide a p -type oxide semiconductor, which has conductivity properties usable as an active layer of a semiconductor element.
- FIG. 1 is a schematic diagram illustrating one example of a diode.
- FIG. 2 is a schematic diagram illustrating one example of a top contact/ bottom gate field-effect transistor.
- FIG. 3 is a schematic diagram illustrating one example of a bottom contact/ bottom gate field-effect transistor.
- FIG. 4 is a schematic diagram illustrating one example of a top contact/ top gate field-effect transistor.
- FIG. 5 is a schematic diagram illustrating one example of a bottom contact/ top gate field-effect transistor.
- FIG. 6 is a diagram for explaining an image display element.
- FIG. 7 is a diagram for illustrating one example of the display element of the present invention.
- FIG. 8 is a schematic diagram illustrating one example of a positional relationship between an organic EL element and a field-effect transistor in a display element.
- FIG. 9 is a schematic diagram illustrating another example of a positional relationship between an organic EL element and a field-effect transistor in a display element.
- FIG. 10 is a schematic diagram illustrating one example of an organic EL element.
- FIG. 11 is a diagram for explaining a display control device.
- FIG. 12 is a diagram for explaining a liquid crystal display.
- FIG. 13 is a diagram for explaining the display element of FIG. 12.
- the p-type oxide semiconductor of the present invention contains a metal oxide containing thallium (Tl), where the metal oxide has been hole doped.
- the hole density of the p -type oxide semiconductor of the present invention is controlled by hole doping, and high mobility is realized since the oxide contains Tl.
- the hole density is preferably controlled in the range of 10 10 /cm 3 to 10 21 /cm 3 , more preferably 10 12 /cm 3 to
- One of methods for performing the hole doping on the metal oxide is to realize oxygen excess (or, cation-deficient) nonstoichiometry. To this end, it is effective to control the conditions when the p-type oxide semiconductor is produced.
- holes can be generated, for example, by optimizing formulation of raw materials, and an atmosphere during the film formation.
- holes can be generated, for example, by optimizing formulation of raw materials, and temperature, duration, and atmosphere during the baking process.
- Tl does not change to divalent even when oxygen is added excessively in a state containing Tl + (a state where one 6p electron is lost).
- a valence modification is caused only when oxidation is progressed until trivalent (a state where one 6p electron and two 6s electrons are lost) .
- Tl + hardly causes a valence modification compared to Cu + , and therefore it is possible to control the hole density in a wide range.
- conductivity properties required are typically different depending on a type or properties of a semiconductor element.
- a hole density can be controlled in a wide range. Therefore, required conductivity properties can be easily realized, which leads to improvement of performance of the semiconductor element.
- Another method of the hole doping is substitutional doping. Part of cations in the metal oxide is substituted with cations having smaller ionic valency, to thereby generate holes depending on a difference in the valency.
- Tl is preferably in a + 1 valent state. In this case, Tl + cannot be substituted with cation havin smaller valency.
- a preferable embodiment is that the p-type oxide semiconductor contains another cation in addition to Tl, and substitutional doping is performed on that cation.
- hole doping can be performed by substituting part of oxygen sites in the metal oxide with anions having smaller ionic valency (i.e., the ionic valency is -3 or smaller) .
- the ionic valency is -3 or smaller
- a valence band peak is delocalized. Specifically, it is preferred that the valence band peak be mainly composed of the 6s orbital of Tl. Other than the +1 valent state, Tl can be in a +3 valent state where one 6p electron and two 6s electrons are lost. In view of improving p-type conductivity properties, all Tl present in the p -type oxide semiconductor is preferably in the + 1 valent state, rather than a state where +1 valent and +3 valent states are mixed.
- the stable conductivity properties thereof become more stable.
- the stable conductivity properties thereof lead to stable operation of a semiconductor element using the p-type oxide semiconductor as an active layer.
- a valence band peak is composed of a hybrid orbital of a 3d orbital of Cu and a 2p orbital of 0, and therefore anisotropy of the electron orbital thereof is strong.
- carriers travel through a band composed of an isotropic 6s orbital of Tl + , and therefore conductivity properties are not influenced by crystallinity.
- the p-type oxide semiconductor of the present invention may be amorphous. Alternatively, part of, or the entire p-type oxide semiconductor may be crystalline. As described earlier, the valence band peak is composed of an isotropic 6s orbital of Tl + , and therefore conductivity properties are not influenced by crystallinity.
- the p -type oxide semiconductor of the present invention may contain an element other than Tl and O.
- the p-type oxide semiconductor may be a composite oxide containing one or more metal elements other than Tl.
- the metal element other than Tl is preferably an element that is stably present with a certain valency. As described above, all of Tl is preferably in the +1 valent state. If the metal element other than Tl can create several valency states, a +1 valent state and a +3 valent state of Tl may be present together. Specific examples of elements that would create a state of several valences include transition metal elements. It is preferred that the p -type oxide semiconductor do not contain these elements.
- the p-type oxide semiconductor do not contain a transition metal element, such as Fe and Cu.
- the p -type oxide semiconductor preferably contains at least one selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), and tellurium (Te). Additionally or
- the p-type oxide semiconductor preferably contains at least one selected from the group consisting of tin (Sn), antimony (Sb), lead (Pb), and bismuth (Bi) .
- the state density of the band, and conductivity properties are controlled in wide ranges by adjusting a type and amount of a counter cation to Tl.
- the metal oxide preferably contains
- TIAIO2 and TlGaO 2 each have a TlFe02 crystal structure, as they are crystallized.
- the metal oxide has this crystal structure.
- the amount by mole of thallium (Tl) contained in the metal oxide is preferably substantially equal to a total amount by mole of aluminum (Al) and gallium (Ga) contained in the metal oxide.
- TlFeO2 crystal structure is easily realized.
- the phrase "substantially equal” means, for example, that a molar ratio ⁇ - ⁇ , where the amount by mole of Tl is X and the total amount by mole of Al and Ga is Y, is in the range of 1.0:0.9 to 1.0-1.1.
- substitutional doping is one of the methods of the hole doping.
- the p-type oxide semiconductor contains a cation other than Tl, and this cation is substituted with a cation having a smaller valency.
- substitutional doping it is necessary that local structure is maintained. If local structural change occurs when it is doped, the dopant may be settled in a stable local structure and does not generate carriers. Accordingly,
- substitutional doping is effective for the metal oxide having high crystallinity, or the metal oxide containing at least a
- the oxide containing Tl, Al, and Ga which has a
- TlFeO2 crystal structure is an embodiment suitable for
- a shape of the p-type oxide semiconductor is appropriately selected depending on the intended purpose without any
- the p-type oxide semiconductor is useful as a p-type active layer of a semiconductor element, such as a p-n junction diode, a PIN photodiode, a field-effect transistor, light emitting element, and photoelectric conversion element.
- a semiconductor element such as a p-n junction diode, a PIN photodiode, a field-effect transistor, light emitting element, and photoelectric conversion element.
- composition for producing a p -type oxide The composition for producing a p -type oxide
- the composition for producing p-type oxide semiconductor is a composition used for production of the p-type oxide
- the solvent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include toluene, xylene, 2-ethyl hexanoic acid, acetyl acetone, ethylene glycol, and 2-methoxy ethanol.
- a solvent such as diethylene glycol, and dimethyl formamide, may also be used.
- An amount of the solvent in the composition for producing a p-type oxide semiconductor is appropriately selected depending on the intended purpose without any limitation.
- the Tl-containing compound is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ organic thallium carboxylates, such as thallium (I) formate, thallium (I) acetate, thallium (I) malonate, and thallium (I) 2-ethylhexanoate, " inorganic salts, such as thallium (I) nitrate, and thallium (I) chloride, ' an organic thallium complexes; and thallium alkoxides, such as thallium ethoxide.
- organic thallium carboxylates such as thallium (I) formate, thallium (I) acetate, thallium (I) malonate, and thallium (I) 2-ethylhexanoate
- inorganic salts such as thallium (I) nitrate, and thallium (I) chloride, ' an organic t
- composition for producing a p-type oxide semiconductor is to be produced with a nonpolar solvent
- organic thallium carboxylate is preferable among them, and thallium (I) 2-ethylhexanoate is more preferable, in view of solubility.
- an inorganic salt is preferable, and thallium (I) nitrate is more preferable, in view of solubility.
- thallium (III) nitrate or thallium (III) chloride is also preferable.
- composition for producing a p -type oxide semiconductor is appropriately selected depending on the intended purpose without any limitation.
- composition for producing a p-type oxide The composition for producing a p-type oxide
- semiconductor preferably further contains a compound, which contains at least one selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), and tellurium (Te).
- Mg magnesium
- Ca calcium
- Ba barium
- Zn zinc
- Cd cadmium
- B aluminum
- Al gallium
- Ga silicon
- germanium germanium
- Te tellurium
- composition for is a composition for a.
- producing a p -type oxide semiconductor preferably contains a compound, which contains at least one selected from the group consisting of tin (Sn), antimony (Sb), lead (Pb), and bismuth (Bi).
- the method for producing p-type oxide semiconductor contains a coating step, and a heat treatment step, and may further contain other steps according to the necessity.
- the coating step is appropriately selected depending on the intended purpose without any limitation, provided that it contains applying a composition onto a support.
- the composition is the composition for producing a p -type oxide semiconductor of the present invention.
- the support is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a glass substrate.
- the application method is appropriately selected
- a known method such as spin coating, inkjet printing, slit coating, nozzle printing, gravure printing, and micro-contact printing, can be used.
- spin coating is preferable.
- the film of a desired shape can be printed by using an appropriate printing method, such as inkjet printing, and micro contact printing, under appropriate printing conditions, and patterning in a later step is not necessary in those cases.
- the heat treatment step contains performing a heat treatment after the coating step.
- the heat treatment step is appropriately selected depending on the intended purpose without any limitation, provided that it is a step capable of drying the solvent in the composition, decomposing the Tl-containing compound, and generating the p-type oxide semiconductor.
- drying of the solvent referred as a "drying treatment” hereinafter
- decomposition of the Tl-containing compound and generation of the p-type oxide semiconductor referred as a “decomposition and generation treatment” hereinafter
- the temperature be elevated to perform the decomposition of the Tl-containing compound, and the generation of the p -type oxide semiconductor.
- the temperature of the drying treatment is not
- the temperature thereof is 80°C to 180°C. It is also effective to use a vacuum oven in the drying process to reduce the temperature.
- the duration of the drying treatment is appropriately selected depending on the intended purpose without any limitation.
- the duration thereof is 10 minutes to 2 hours.
- the temperature of the decomposition and generation treatment is appropriately selected depending on the intended purpose without any limitation.
- the temperature thereof is 200°C to 400°C.
- the duration of the decomposition and generation treatment is appropriately selected depending on the intended purpose without any limitation.
- the duration thereof is 1 hour to 5 hours.
- a method of the heat treatment step is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a method of heating the support.
- the atmosphere of the heat treatment step is
- the heat treatment step it is effective to irradiate the composition after the drying treatment with ultraviolet rays having a wavelength of 400 nm or shorter, to accelerate a reaction of the decomposition and generation treatment.
- ultraviolet rays having a wavelength of 400 nm or shorter bond cleavage occurs in chemical bonds of organic materials, and the organic materials are decomposed, and thus the p-type oxide semiconductor can be efficiently produced.
- the ultraviolet rays having a wavelength of 400 nm or shorter are appropriately selected depending on the intended purpose without any limitation, and examples thereof include ultraviolet rays having a wavelength of 222 nm, emitted from an excimer lamp.
- ozone instead of, or in combination with the radiation of the ultraviolet rays.
- the p-type oxide semiconductor In the method for producing a p-type oxide semiconductor according to the present invention, the p-type oxide
- the p-type oxide semiconductor is produced through a coating process. Compared to a production through a vacuum process, the p-type oxide semiconductor can be produced easily, with a large quantity, and at low cost.
- the method for producing a p-type oxide semiconductor can produce the p -type oxide semiconductor having excellent p-type conductivity.
- a constituent of the p-type oxide semiconductor specifically, a Tl content, a type of metal elements other than Tl, and amounts thereof.
- a constituent of the p-type oxide semiconductor specifically, a Tl content, a type of metal elements other than Tl, and amounts thereof.
- metal-containing compound should be changed. Moreover, one of methods of hole doping is to realize oxygen excess
- nonstoichiometry The difference from stoichiometry of O can be controlled by varying various conditions, such as temperature, duration, and atmosphere of the heat treatment step .
- a compound containing a metal to be added by the substitutional doping is blended at the predetermined ratio when the
- composition is prepared. In the manner as described above, hole doping is easily realized, and conductivity properties are controlled. As a result, an oxide semiconductor having desired p-type conductivity is attained.
- the semiconductor element of the present invention contains at least an active layer, and may further contain other members according to the necessity.
- the active layer is appropriately selected depending on the intended purpose without any limitation, provided that the active layer contains the p-type oxide semiconductor of the present invention.
- the p-type oxide semiconductor of the present invention Since the p -type oxide semiconductor of the present invention has excellent stability, and conduction properties of which are easily controlled depending on the intended purpose, as described above, the p-type oxide semiconductor of the present invention is suitable for use as an active layer of the
- semiconductor element can be improved by adding the p-type oxide semiconductor whose properties are optimized to the active layer.
- a structure, shape, and size of the active layer are appropriately selected depending on the intended purpose without any limitation.
- Examples of the semiconductor element include a diode, a field-effect transistor, a light emitting element, and a
- a type of the diode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a diode, which contains a first electrode, a second electrode, and the active layer formed between the first electrode and the second electrode.
- examples of such a diode include a p -n junction diode, and a PIN photodiode.
- the p-n junction diode contains at least the active layer, and may further contain other members, such as an anode
- the active layer contains at least a p -type semiconductor layer, and an n-type semiconductor layer, and may further contain other members according to the necessity.
- semiconductor layer are in contact with each other.
- a material of the p-type semiconductor layer is
- a constituent or formation conditions of the p-type oxide semiconductor be selected to attain a carrier density and carrier mobility required for functioning as the active layer.
- the average thickness of the p-type semiconductor layer is appropriately selected depending on the intended purpose without any limitation, but the average thickness thereof is preferably 50 nm to 2,000 nm.
- a material of the n-type semiconductor layer is
- the material thereof is preferably an n-type transparent oxide semiconductor.
- n-type oxide semiconductor is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ZnO, and IGZO (In-Ga-Zn-O).
- a formation method of the n-type semiconductor layer is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ a vacuum process, such as sputtering, pulse laser deposition (PLD), CVD, and ALD; and a printing method, such as dip coating, inkjet printing, and nanoimprinting.
- a vacuum process such as sputtering, pulse laser deposition (PLD), CVD, and ALD
- PLD pulse laser deposition
- ALD atomic layer deposition
- a printing method such as dip coating, inkjet printing, and nanoimprinting.
- the average thickness of the n-type semiconductor layer is appropriately selected depending on the intended purpose without any limitation, but the average thickness thereof is preferably 50 nm to 2,000 nm.
- an excellent electrical connection be established between the p-type semiconductor layer and the n-type semiconductor layer.
- a conventional p-type oxide containing Cu is used as a p -type semiconductor layer of a p-n junction diode
- an excellent electric connection may not be attained when a mismatch of lattic with the n-type semiconductor layer occurs, since the orbital constituting the valence band peak (hybrid orbital of a 3d orbital of Cu and a 2p orbital of O) is anisotropic.
- the p-type oxide semiconductor of the present invention is used as a p-type semiconductor layer, an influence of the aforementioned lattice mismatch is hardly received, as the valence band peak is composed of a 6s orbital of Tl + , which is isotropic and has a large orbital radius. Therefore, an excellent electrical connection state is easily realized.
- semiconductor layer consists of an n-type oxide (e.g., IGZO, ⁇ 2 ⁇ 3 , and Sn02) having an s orbital of a cation, such as In and Sn, at the bottom end of the conduction band, it is preferable to use the p-type oxide of the present invention as a p-type semiconductor layer since isotropic s orbitals are used for transporting carriers in the both n-type and p-type semiconductor layers in that case and excellent electrical connection can be established.
- n-type oxide e.g., IGZO, ⁇ 2 ⁇ 3 , and Sn02
- the anode is in contact with the p -type semiconductor layer.
- a material of the anode is appropriately selected
- ⁇ metal such as Mo, Al, Au, Ag, and Cu
- antimony-doped tin oxidei and organic conductors such as polyethylene dioxythiophene (PEDOT), and polyaniline (PANI).
- PEDOT polyethylene dioxythiophene
- PANI polyaniline
- a shape, size, and structure of the anode are appropriately selected depending on the intended purpose without any
- the anode is provided in contact with the p-type
- a formation method of the anode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include - (i) a method where after forming a film through sputtering or dip coating, the film is patterned by photolithography! and (ii) a method where a film of a desired shape is directly formed by a printing process, such as inkjet printing, nanoimprinting, and gravure printing.
- a material of the cathode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include those listed as the material of the anode in the descriptions of the anode.
- a shape, size, and structure of the cathode are
- the cathode is provided in contact with the n-type semiconductor layer. It is preferred that the cathode and the n-type semiconductor layer form an ohmic contact.
- a formation method of the cathode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include those methods listed as the formation method in the descriptions of the anode.
- a cathode 2 is formed on a base material 1.
- a shape, structure, and size of the base material are appropriately selected depending on the intended purpose without any limitation.
- a base material is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a glass substrate, and a plastic substrate.
- a material of the glass substrate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include non-alkali glass, and silica glass.
- a material of the plastic substrate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include polycarbonate (PC), polyimide (PI), polyethylene terephthalate (PET), and
- PEN polyethylene naphthalate
- the base material is preferably subjected to a pretreatment, such as oxygen plasma cleaning, UV ozone cleaning, and UV radiation washing, in order to clean a surface thereof, and improve adhesion.
- a pretreatment such as oxygen plasma cleaning, UV ozone cleaning, and UV radiation washing
- an n-type semiconductor layer 3 is formed on the cathode 2.
- a p-type semiconductor layer 4 is formed on the n-type semiconductor layer 3.
- an anode 5 is formed on the p -type
- the field-effect transistor contains at least a gate electrode, a source electrode, a drain electrode, an active layer, and a gate insulating layer, and may further contain other members according to the necessity.
- the gate electrode is appropriately selected depending on the intended purpose without any limitation, provided that it is an electrode configured to apply gate voltage.
- a material of the gate electrode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ a metal, such as Mo, Al, Au, Ag, and Cu, ' an alloy of any of the aforementioned metals! transparent conductive oxides, such as indium tin oxide (ITO), and
- ATO antimony-doped tin oxide
- organic conductors such as polyethylene dioxythiophene (PEDOT), and polyaniline (PANT) .
- a formation method of the gate electrode is appropriately selected depending on the intended purpose without any
- the gate electrode is appropriately selected depending on the intended purpose without any limitation, but the average thickness thereof is preferably 20 nm to 1 ⁇ , more preferably 50 nm to 300 nm.
- the source electrode and the drain electrode are the same.
- a material of the source electrode and drain electrode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include those materials listed in the descriptions of the gate electrode.
- the source electrode and the drain electrode a material that will give a small contact resistance be selected as the source electrode and the drain electrode. Specifically, it is preferred that a material having a larger work function than that of the p-type oxide semiconductor of the present invention contained in the active layer be selected.
- a formation method of the source electrode, and the drain electrode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include those listed as the formation method in the descriptions of the gate electrode.
- the average thickness of the source electrode and the drain electrode is appropriately selected depending on the intended purpose without any limitation, but the average thickness thereof is preferably 20 nm to 1 ⁇ , more preferably 50 nm to 300 nm.
- the active layer contains the p-type oxide semiconductor of the present invention.
- the active layer is formed between the source electrode and the drain electrode.
- the "between” is a position where the active layer can operate the field-effect transistor together with the source electrode and the drain electrode.
- the position of the active layer is appropriately selected depending on the intended purpose without any limitation, as long as it is the aforementioned position.
- composition or formation conditions of the p-type oxide semiconductor is preferably selected in a manner that the carrier density and carrier mobility required to function as the active layer are attained.
- the average thickness of the active layer is appropriately selected depending on the intended purpose without any
- the average thickness thereof is preferably 5 nm to 1 ⁇ , more preferably 10 nm to 300 nm.
- the gate insulating layer is appropriately selected depending on the intended purpose without any limitation, provided that it is an insulating layer formed between the gate electrode and the active layer.
- a material of the gate insulating layer is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ materials that have been widely used in mass production, such as Si02, and SiNxi high dielectric constant materials, such as La2O3, and Hf02> ' and organic materials, such as polyimide (PI), and a fluororesin.
- PI polyimide
- a formation method of the gate insulating layer is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ a vacuum film formation method, such as sputtering, chemical vapor deposition (CVD), and atomic layer deposition (ALD); and a printing method, such as spin coating, die coating, and inkjet printing.
- a vacuum film formation method such as sputtering, chemical vapor deposition (CVD), and atomic layer deposition (ALD)
- a printing method such as spin coating, die coating, and inkjet printing.
- the average thickness of the gate insulating layer is appropriately selected depending on the intended purpose without any limitation, but the average thickness thereof is preferably 50 nm to 3 ⁇ , more preferably 100 nm to 1 ⁇ .
- a structure of the field-effect transistor is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a top contact/bottom gate structure (FIG. 2), a bottom contact/ bottom gate structure (FIG. 3), a top contact/ top gate structure (FIG. 4), and a bottom contact/ top gate structure (FIG. 5).
- 21 is a substrate
- 22 is an active layer
- 23 is a source electrode
- 24 is a drain electrode
- 25 is a gate insulating layer
- 26 is a gate electrode.
- the field-effect transistor is suitably used for a display element, which is described later, but use thereof is not limited to the display element.
- the field-effect transistor is suitably used for an IC card, or an ID tag.
- the field-effect transistor uses the p-type oxide semiconductor of the present invention in an active layer thereof, the active layer of preferable properties is realized, and the transistor characteristics thereof are stable and excellent.
- a gate electrode is formed on a substrate.
- a shape, structure, and size of the substrate are
- a material of the substrate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a glass substrate, and a plastic substrate.
- a material of the glass substrate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include non-alkali glass, and silica glass.
- a material of the plastic substrate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include polycarbonate (PC), polyimide (PI), polyethylene terephthalate (PET), and
- PEN polyethylene naphthalate
- the substrate is preferably subjected to a pretreatment, such as oxygen plasma cleaning, UV ozone cleaning, and UV radiation washing, in order to clean a surface thereof, and improve adhesion.
- a pretreatment such as oxygen plasma cleaning, UV ozone cleaning, and UV radiation washing
- the gate insulating layer is formed on the gate electrode.
- an active layer containing the p-type oxide semiconductor is formed at the area that is in a channel region, and on the gate insulating layer.
- a source electrode and a drain electrode are formed separately from each other on the gate insulating layer in a manner that the source electrode and the drain electrode step over the active layer.
- a field-effect transistor is produced.
- a top contact/ bottom gate field-effect transistor for example, as illustrated in FIG. 2, is produced. ⁇ . - (Display Element)
- the display element of the present invention contains at least a light control element, and a driving circuit configured to drive the light control element, and may further contain other members, according to the necessity.
- the light control element is appropriately selected depending on the intended purpose without any limitation, provided that it is an element configured to control light outlet according to a driving signal.
- Examples thereof include an organic electroluminescent (EL) element, an electrochromic (EC) element, a liquid crystal element, an electrophoretic element, and an electrowetting element.
- the driving circuit is appropriately selected depending on the intended purpose without any limitation, provided that the driving circuit contains the semiconductor element of the present invention.
- the display element of the present invention contains the semiconductor element (e.g., the field-effect transistor) of the present invention, the display element operates stably. Even when the properties of the light control elements change with time, a driving transistor can be operated at constant gate electrode, which leads to a long service life of the display element.
- the semiconductor element e.g., the field-effect transistor
- the image display device of the present invention contains at least a plurality of display elements, a plurality of lines, and a display control device, and may further contain other members according to the necessity.
- the display elements are appropriately selected depending on the intended purpose without any limitation, provided that they are the display elements of the present invention, which are arranged in a matrix.
- the lines are appropriately selected depending on the intended purpose without any limitation, provided that they are capable of separately applying gate voltage and an image data signal to each of field-effect transistors in each of the display elements.
- the display control device is appropriately selected depending on the intended purpose without any limitation, provided that it is capable of controlling the gate voltage and the signal voltage of each of the field-effect transistors through the lines according to the image data.
- the image display device of the present invention contains the display element of the present invention, the image display device operates stably with long service life.
- the image display device of the present invention can be used as a display unit in a mobile information device (e.g., a mobile phone, a portable music player, a portable video player, an electronic book, and a personal digital assistant (PDA), or a camera device (e.g., a still camera, and a video camera).
- a mobile information device e.g., a mobile phone, a portable music player, a portable video player, an electronic book, and a personal digital assistant (PDA), or a camera device (e.g., a still camera, and a video camera).
- PDA personal digital assistant
- the image display device can also be used as a display unit for various types of information in a transport system, such as a car, an air craft, a train, and a ship. Furthermore, the image display device can be used as a display unit for various types of information in a measuring device, an analysis device, medical equipment, or advertising media.
- the system of the present invention contains at least the image display device of the present invention, and an image data generating device.
- the image data generating device is configured to generate image data based on image information to be displayed, and to output the image data to the image display device. Since the system of the present invention contains the image display device of the present invention, the system can display image information stably with high performance.
- the image display device of the present invention is explained next.
- the structure disclosed in the paragraphs [0059] to [0060], and FIGs. 2 and 3 of JP-A No. 2010-074148 can be used.
- FIG. 6 is a diagram illustrating a display where display elements are arranged in a matrix.
- the display contains "n" number of scanning lines (X0, XI, X2, X3, ... Xn-2, Xn- l) arranged along the X axis direction with a constant interval, "m" number of data lines (Y0, Yl, Y2, Y3, ... Ym- l) arranged along the Y axis direction with a constant interval, and "m” number of current supply lines (YOi, Yli, Y2i, Y3i, ...Ym- li) arranged along the Y axis direction with a constant interval.
- the same reference number e.g., XI, Yl
- the display element 302 can be specified with the scanning line and the data line.
- FIG. 7 is a schematic diagram illustrating one example of the display element of the present invention.
- the display element contains an organic electroluminescent (EL) element 350, and a driving circuit 320 configured to induce emission of the organic EL element 350.
- the display 310 is a so-called active matrix organic EL display.
- the display 310 is a 32-inch color display. Note that, a size of the display is not limited to the aforementioned size .
- the driving circuit 320 of FIG. 7 is explained.
- the driving circuit 320 contains two field-effect
- transistors 10 and 20 and a capacitor 30.
- the field-effect transistor 10 functions as a switching element.
- the gate electrode G of the field-effect transistor 10 is connected to the predetermined scanning line, and the source electrode S of the field-effect transistor 10 is connected to the predetermined data line.
- the drain electrode D of the field-effect transistor 10 is connected to one of the two terminals of the capacitor 30.
- the field-effect transistor 20 is configured to supply electric current to the organic EL element 350.
- the gate electrode G of the field-effect transistor 20 is connected to the drain electrode D of the field-effect transistor 10.
- the drain electrode D of the field-effect transistor 20 is connected to the anode of the organic EL element 350, and the source electrode D of the field-effect transistor 20 is connected to the predetermined electric current supply line .
- the capacitor 30 is configured to store a state of the field-effect transistor 10, i.e., data. Another terminal of the capacitor 30 is connected to the predetermined electric current supply line.
- the field-effect transistor 10 As the field-effect transistor 10 is turned in the state of "On,” the image data is stored in the capacitor 30 via the signal line Y2. Even after turning the field-effect transistor 10 to the state of "Off,” the field-effect transistor 20 is maintained in the state of "On” corresponding to the image data so that the organic EL element 350 is driven.
- FIG. 8 illustrates one example of a positional relationship between the organic EL element 350 and the field-effect transistor 20 serving as a driving circuit in the display element.
- the organic EL element 350 is provided next to the field-effect transistor 20.
- the field-effect transistor and a capacitor are formed on the same substrate.
- a protective film be formed on top of the active layer 22.
- a material of the protective film S1O2, SiNx, AI2O3, or a fluoropolymer is appropriately used.
- the organic EL element 350 may be formed above the field-effect transistor 20.
- the gate electrode 26 needs to be transparent.
- transparent conductive oxides such as ITO, ⁇ ⁇ 2 ⁇ 3, SnO2, ZnO, Ga-doped ZnO, Al-doped ZnO, and Strdoped SnO2, are used.
- the reference number 360 represents an interlayer insulating film (a leveling film).
- the interlayer insulating film polyimide, or an acrylic resin can be used.
- the field-effect transistor 20 contains a substrate 21, an active layer 22, a source electrode 23, a drain electrode 24, a gate insulating layer 25, and a gate electrode 26.
- the organic EL element 350 contains a cathode 312, an anode 314, and an organic EL thin film layer 340.
- FIG. 10 is a schematic diagram illustrating one example of the organic EL element.
- the organic EL element 350 contains a cathode 312, an anode 314, and an organic EL thin film layer 340.
- a material of the cathode 312 is appropriately selected depending on the intended purpose without any limitation, and examples thereof include aluminum (Al), magnesium (Mg) -silver (Ag) alloy, aluminum (Al) -lithium (Li) alloy, and indium tin oxide (ITO).
- Al aluminum
- Mg magnesium
- Al aluminum
- Al aluminum
- Li lithium
- ITO indium tin oxide
- the magnesium (Mg)-silver (Ag) alloy films with a sufficient thickness forms a high reflectance electrode, and an extremely thin film (less than about 20 nm) thereof forms a semi-transparent electrode.
- FIG. 10 light is taken out from the side of the anode. However, light can be taken out from the side of the cathode by making the cathode a transparent or semi-transparent.
- a material of the anode 314 is appropriately selected depending on the intended purpose without any limitation, and examples thereof include indium tin oxide (ITO), indium zinc oxide (IZO), and silver (Ag)-neodymium (Nd) alloy. Note that, in the case where the silver alloy is used, a resulting electrode becomes a high reflectance electrode, which is suitable for taking light out from the side of the cathode.
- the organic EL thin film layer 340 contains an electron transporting layer 342, a light emitting layer 344, and a hole transporting layer 346.
- the electron transporting layer 342 is connected to the cathode 312, and the hole transporting layer 346 is connected to the anode 314.
- the predetermined voltage is applied between the anode 314 and the cathode 312, the light emitting layer 344 emits light.
- the electron transporting layer 342 and the light emitting layer 344 may form one layer.
- an electron injecting layer may be provided between the electron
- a hole injecting layer may be provided between the hole
- FIG. 11 is a schematic diagram illustrating another example of the image display device of the present invention.
- the image display device contains a display element 302, lines (scanning lines, data lines, and electric current supply lines), and a display control device 400.
- the display control device 400 contains an image data processing circuit 402, a scanning line driving circuit 404, and a data line driving circuit 406.
- the image data processing circuit 402 judges luminance of a plurality of the display elements 302 based on output signal of the image output circuit.
- the scanning line driving circuit 404 individually applies voltage to the number "n" of scanning lines according to the instructions of the image data processing circuit 402.
- the data line driving circuit 406 individually applies voltage to the number "m" of data lines according to the
- the light control element is an organic EL element, but the light control element is not limited to the organic EL element.
- the light control element may be an electrochromic element.
- the display is an electrochromic display.
- the light control element may be a liquid crystal element.
- the display is a liquid crystal display, and a current supply line is not necessary to the display element 302' as illustrated in FIG. 12.
- the driving circuit 320' may be composed of one field-effect transistor 40, which is identical to the field-effect transistors 10 and 20. In the field-effect transistor 40, the gate electrode G is connected to the predetermined scanning line, and the source electrode S is connected to the predetermined data line.
- drain electrode D is connected to the capacitor 361 and a pixel electrode of the liquid crystal element 370.
- the light control element may be an
- electrophoretic element an inorganic EL element, or an
- the system of the present invention is a television device
- the system is not limited as long as the system contains the image display device as a device for displaying images and information.
- the system may be a computer system, in which a computer
- the image display device (including a personal computer) is connected to the image display device.
- the system of the present invention contains the image display device of the present invention, the system operates stably with a long-service life.
- Thallium 2-ethylhexanoate (695.2 mg) was dissolved in 2 mL of toluene, to thereby obtain a thallium compound solution A.
- the molar concentration of the thallium (Tl) in the thallium compound solution A was 1 M.
- compound solution B was 0.1 M.
- 2-ethylhexanoate which was a 3.0% by mass zinc (equivalent to 0.404 M) solution, to 1.505 mL of toluene, a zinc compound solution C was obtained.
- the molar concentration of the zinc (Zn) in the zinc compound solution C was 0.1 M.
- Hexamethyl disilazane (0.104 mL) was diluted with 9.896 mL of toluene, to thereby obtain a silicon compound solution D.
- compound solution D was 0.1 M.
- Phenylboronic acid pinacol ester (204.1 mg) was dissolved in 2 mL of toluene, to thereby obtain a boron compound solution E.
- the molar concentration of the boron (B) in the boron compound solution E was 0.5 M.
- Tellurium (IV) isopropoxide (0.364 mL) was diluted with 10 mL of toluene, to thereby obtain a tellurium compound solution F.
- the molar concentration of tellurium (Te) in the tellurium compound solution F was 0.1 M.
- Gallium acetylacetonate (183.5 mg) was dissolved in 2 mL of toluene, to thereby obtain a gallium compound solution G.
- the molar concentration of the gallium (Ga) in the gallium compound solution G was 0.25 M.
- Aluminum acetylacetonate (162.2 mg) was dissolved in 2 mL of toluene, to thereby obtain an aluminum compound solution H.
- the molar concentration of the aluminum (Al) in the aluminum compound solution H was 0.25 M.
- Tin 2-ethylhexanoate (0.341 mL) having the purity of 95% by mass and 1.659 mL of toluene were blended, to thereby obtain a tin compound solution I.
- the molar concentration of the tin (Sn) of the tin compound solution I was 0.5 M.
- Triphenylantimony 353.1 mg was dissolved in 2 mL of toluene, to thereby obtain an antimony compound solution J.
- the molar concentration of the antimony (Sb) of the antimony compound solution J was 0.5 M.
- Lead 2-ethylhexanoate (0.333 mL) and 1.667 mL of toluene were blended, to thereby obtain a lead compound solution K.
- the molar concentration of the lead (Pb) in the lead compound solution K was 0.5 M.
- 2-ethylhexanoate which was a 24% by mass bismuth (equivalent to 1.033 M) solution, to 0.968 mL of toluene, a bismuth compound solution L was obtained.
- the molar concentration of the bismuth (Bi) of the bismuth compound solution L was 0.5 M.
- compositions for producing a p-type oxide semiconductor having formulations depicted in Table 1 were prepared.
- each of the 15 inks was spin coated onto a glass substrate. After drying the ink at 120°C for 1 hour, the ink was baked at 250°C for 3 hours while applying light with an excimer lamp (wavelength: 222 nm) under a nitrogen flow having the oxygen concentration of 0.1 ppm to 0.3 ppm, to thereby form Tl-containing oxide films (p-type oxide semiconductor film) of the 15 formulations.
- an excimer lamp wavelength: 222 nm
- the ink for Cu oxide was applied onto a glass substrate by spin coating, followed by drying the ink at 120°C for 1 hour.
- the ink was baked at 250°C for 3 hours while applying light to the ink with an excimer lamp (wavelength- 222 nm) under a flow of nitrogen.
- a reflection spectrum (wavelength: about 300 nm to about
- Comparative Example 1 was subjected to X-ray diffraction spectroscopy by means of X'PertPro (manufactured by Philips).
- the strongest peak appeared at 2 ⁇ of about 29 degrees, and the second strongest peak appeared between about 32 degrees and about 34 degrees.
- the strongest peak appeared at 2 ⁇ of about 36 degrees, and the peaks having the smaller intensities were observed at about 39 degrees, about 42 degrees, and about 61 degrees.
- the peak at the about 39 degrees corresponds to a CuO crystal, and the peaks at about 42 degrees and about 61 degrees correspond to a CU2O crystal. It was considered that the peak at about 36 degrees was observed as peaks from both a CuO crystal and a CU2O crystal, without being separated. It was found from the results above that the
- Cu oxide film was in a polycrystalline state where CuO crystals and Cu 2 O crystals were mixed.
- Examples 8 and 11, and Tl(Alo.5Gao.5) O2 in Example 9, provided that the oxygen content was excessive in terms of a difference from stoichiometry.
- the Tl in each film was in the monovalent state.
- the electric properties thereof were p -type using holes as carriers.
- the films of Examples 10, and 12 to 15 were
- the obtained film was a polycrystalline film, in which a CuO crystal and a CU2O crystal were mixed, as seen from the result of X-ray diffraction.
- the measurement of the carrier density or judgment of conductivity could not be performed, as the resistivity was too high.
- the volume resistivity of the active layer in the semiconductor element was greater than 10 8 Qcm, it is difficult to attain ohmic contact with an electrode conntected to the semiconductor.
- the film of Comparative Example 1 was therefore not suitable for applicable use as an active layer.
- the oxide film of the present invention which contained Tl and had been hole doped, could attain the
- the conventional Cu oxide film could not attain useful p-type conductivity properties, as two valence stages Cu were present together.
- a Si substrate with a thermally oxidized film (thickness ' - 200 nm) was used.
- the Si substrate was subjected to ultrasonic wave washing using a neutral detergent, pure water, and isopropyl alcohol. After drying, the substrate was further subjected to a UV-ozone treatment at 90°C for 10 minutes. Note that, the thermally oxidized film served as a gate insulating layer, and the Si substrate served as a gate electrode.
- T1A1 ink O a semiconductor ink for inoket printing
- the T1A1 ink O was applied to the predetermined area of the substrate, on which the source electrode and drain electrode had been formed, by means of an inkjet printing. After drying the ink at 120°C for 1 hour, the ink was baked at 250°C for 3 hours, while applying light with an excimer lamp (wavelength: 222 nm), to thereby form a T1A1 oxide film having a thickness of 30 nm. As a result of this, a structure of a field-effect transistor was completed.
- a field-effect transistor was produced in the same manner as in Example 16, provided that the semiconductor ink was replaced with the following semiconductor ink (TISb ink R).
- the molar ratio of Tl and Sb in the ink was 1 : 1.
- the embodiments of the present invention are, for example, as follows.
- a p-type oxide semiconductor containing:
- ⁇ 2> The p-type oxide semiconductor according to ⁇ 1>, wherein the metal oxide contains magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), or tellurium (Te), or any combination thereof.
- ⁇ 3> The p-type oxide semiconductor according to ⁇ 1> or ⁇ 2>, wherein the metal oxide contains tin (Sn), antimony (Sb), lead (Pb), or bismuth (Bi), or any combination thereof.
- ⁇ 4> The p-type oxide semiconductor according to any one of ⁇ 1> to ⁇ 3>, wherein the metal oxide contains aluminum (Al), or gallium (Ga), or both.
- composition is used for production of the p-type oxide semiconductor according to any one of ⁇ 1> to ⁇ 5>.
- the p-type oxide semiconductor is the p-type oxide semiconductor according to any one of ⁇ 1> to ⁇ 5>, and
- composition contains a solvent, and a solvent
- the active layer contains the p-type oxide semiconductor according to any one of ⁇ 1> to ⁇ 5>.
- the semiconductor element is a field-effect transistor, which contains: a gate electrode configured to apply gate voltage;
- a source electrode and a drain electrode both of which are configured to take electric currents out;
- a gate insulating layer formed between the gate electrode and the active layer.
- a display element containing:
- a light control element configured to control light output according to a driving signal
- a driving circuit which contains the semiconductor element according to ⁇ 8>, and is configured to drive the light control element.
- the light control element contains an organic electroluminescent element, an electrochromic element, a liquid crystal element, an
- electrophoretic element or an electrowetting element.
- An image display device which displays an image
- a plurality of lines each configured to separately apply gate voltage to field-effect transistors in each of the display elements, ' and a display control device configured to individually control the gate voltage of each of field-effect transistors through the lines according to the image data.
- an image data generating device configured to generate image data based on image information to be displayed, and to output the generated image data to the image display device.
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- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Ceramic Engineering (AREA)
- Nonlinear Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Geometry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Mathematical Physics (AREA)
- Theoretical Computer Science (AREA)
- Thin Film Transistor (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Liquid Crystal (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP2013268915 | 2013-12-26 | ||
JP2014212632A JP6547273B2 (ja) | 2013-12-26 | 2014-10-17 | p型酸化物半導体、p型酸化物半導体製造用組成物、p型酸化物半導体の製造方法、半導体素子、表示素子、画像表示装置、及びシステム |
PCT/JP2014/083814 WO2015098785A1 (fr) | 2013-12-26 | 2014-12-16 | Semiconducteur d'oxyde de type p, composition pour la production d'un semiconducteur d'oxyde de type p, procédé de production d'un semiconducteur d'oxyde de type p, élément à semiconducteurs, élément d'affichage, dispositif d'affichage d'image et système correspondant |
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EP3087614A1 true EP3087614A1 (fr) | 2016-11-02 |
EP3087614A4 EP3087614A4 (fr) | 2017-02-08 |
EP3087614B1 EP3087614B1 (fr) | 2021-02-17 |
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EP14875695.0A Active EP3087614B1 (fr) | 2013-12-26 | 2014-12-16 | Semiconducteur d'oxyde de type p, composition pour la production d'un semiconducteur d'oxyde de type p, procédé de production d'un semiconducteur d'oxyde de type p, élément à semiconducteurs, élément d'affichage, dispositif d'affichage d'image et système correspondant |
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US (1) | US20170301738A1 (fr) |
EP (1) | EP3087614B1 (fr) |
JP (1) | JP6547273B2 (fr) |
KR (1) | KR101824349B1 (fr) |
CN (1) | CN105849914B (fr) |
BR (1) | BR112016015034B1 (fr) |
RU (1) | RU2660407C2 (fr) |
SG (1) | SG11201605254RA (fr) |
TW (1) | TWI672814B (fr) |
WO (1) | WO2015098785A1 (fr) |
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EP4403666A2 (fr) | 2022-05-31 | 2024-07-24 | Imec VZW | Oxydes métalliques mixtes |
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US10115828B2 (en) * | 2015-07-30 | 2018-10-30 | Ricoh Company, Ltd. | Field-effect transistor, display element, image display device, and system |
KR20190022561A (ko) * | 2016-06-30 | 2019-03-06 | 가부시키가이샤 플로스피아 | 산화물 반도체 막 및 그 제조 방법 |
JP6942943B2 (ja) * | 2016-07-22 | 2021-09-29 | 株式会社リコー | 半導体素子の製造方法 |
CN109478110B (zh) * | 2016-09-16 | 2022-04-15 | 凸版印刷株式会社 | 显示装置及显示装置基板 |
US11374054B2 (en) | 2018-03-19 | 2022-06-28 | Ricoh Company, Ltd. | Inorganic el element, display element, image display device, and system |
CN109148593B (zh) * | 2018-07-16 | 2020-09-01 | 复旦大学 | 一种三元p型CuBi2O4薄膜晶体管及其制备方法 |
JP7173070B2 (ja) * | 2020-03-13 | 2022-11-16 | 株式会社村田製作所 | 酸化物半導体素子及び酸化物半導体素子の製造方法 |
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US4240716A (en) * | 1978-12-15 | 1980-12-23 | Bell Telephone Laboratories, Incorporated | Electrodeposition display device |
JPH10284743A (ja) | 1997-04-01 | 1998-10-23 | Sharp Corp | 光電変換素子 |
JP2004079620A (ja) * | 2002-08-12 | 2004-03-11 | National Institute Of Advanced Industrial & Technology | 透明半導体バルク単結晶基板を用いた電子素子 |
JP2004172166A (ja) * | 2002-11-15 | 2004-06-17 | Zenji Hiroi | 光センサー |
WO2004112440A1 (fr) * | 2003-06-13 | 2004-12-23 | Matsushita Electric Industrial Co., Ltd. | Dispositif emetteur de lumiere, procede de production associe et afficheur |
US7026713B2 (en) | 2003-12-17 | 2006-04-11 | Hewlett-Packard Development Company, L.P. | Transistor device having a delafossite material |
CN101553930A (zh) * | 2005-03-30 | 2009-10-07 | 莫克斯特罗尼克斯有限公司 | 金属氧化物半导体薄膜、结构和方法 |
GB2441699B (en) * | 2005-05-14 | 2011-04-06 | Atmos | Metal oxide particles for use as semiconductor materials and methods of producing them |
US20070126021A1 (en) * | 2005-12-06 | 2007-06-07 | Yungryel Ryu | Metal oxide semiconductor film structures and methods |
US8148731B2 (en) * | 2006-08-29 | 2012-04-03 | Moxtronics, Inc. | Films and structures for metal oxide semiconductor light emitting devices and methods |
RU2462793C2 (ru) * | 2007-12-28 | 2012-09-27 | Юниверсите Де Ля Медитерране Экс-Марсель Ii | Гибридные нанокомпозиционные материалы |
WO2010010802A1 (fr) * | 2008-07-24 | 2010-01-28 | 独立行政法人科学技術振興機構 | TRANSISTOR À FILM FIN ET À CANAL P, ET PROCESSUS DE FABRICATION DU TRANSISTOR À FILM FIN ET À CANAL p |
TWI626744B (zh) * | 2008-07-31 | 2018-06-11 | 半導體能源研究所股份有限公司 | 半導體裝置及半導體裝置的製造方法 |
JP5480554B2 (ja) * | 2008-08-08 | 2014-04-23 | 株式会社半導体エネルギー研究所 | 半導体装置 |
TW201030994A (en) * | 2009-02-12 | 2010-08-16 | Nexpower Technology Corp | Two sided light absorbing type solar cell |
JP5506213B2 (ja) | 2009-03-06 | 2014-05-28 | キヤノン株式会社 | 半導体素子の形成方法 |
US8198671B2 (en) * | 2009-04-22 | 2012-06-12 | Applied Materials, Inc. | Modification of charge trap silicon nitride with oxygen plasma |
US8354694B2 (en) * | 2010-08-13 | 2013-01-15 | International Business Machines Corporation | CMOS transistors with stressed high mobility channels |
US20140217470A1 (en) * | 2011-09-08 | 2014-08-07 | Tamura Corporation | Ga2O3 SEMICONDUCTOR ELEMENT |
JP5783094B2 (ja) * | 2011-11-30 | 2015-09-24 | 株式会社リコー | p型酸化物、p型酸化物製造用組成物、p型酸化物の製造方法、半導体素子、表示素子、画像表示装置、及びシステム |
WO2013187486A1 (fr) * | 2012-06-14 | 2013-12-19 | 独立行政法人物質・材料研究機構 | Transistor à film mince, son procédé de production et dispositif à semi-conducteurs |
CN103715234B (zh) * | 2012-09-28 | 2016-05-04 | 财团法人工业技术研究院 | p型金属氧化物半导体材料 |
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- 2014-12-16 SG SG11201605254RA patent/SG11201605254RA/en unknown
- 2014-12-16 KR KR1020167019926A patent/KR101824349B1/ko active IP Right Grant
- 2014-12-16 CN CN201480071319.1A patent/CN105849914B/zh not_active Expired - Fee Related
- 2014-12-16 EP EP14875695.0A patent/EP3087614B1/fr active Active
- 2014-12-16 BR BR112016015034-1A patent/BR112016015034B1/pt not_active IP Right Cessation
- 2014-12-16 RU RU2016130090A patent/RU2660407C2/ru active
- 2014-12-16 WO PCT/JP2014/083814 patent/WO2015098785A1/fr active Application Filing
- 2014-12-16 US US15/107,160 patent/US20170301738A1/en not_active Abandoned
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Cited By (1)
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EP4403666A2 (fr) | 2022-05-31 | 2024-07-24 | Imec VZW | Oxydes métalliques mixtes |
Also Published As
Publication number | Publication date |
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RU2660407C2 (ru) | 2018-07-06 |
WO2015098785A1 (fr) | 2015-07-02 |
JP2015144240A (ja) | 2015-08-06 |
TW201526233A (zh) | 2015-07-01 |
RU2016130090A (ru) | 2018-01-31 |
SG11201605254RA (en) | 2016-07-28 |
TWI672814B (zh) | 2019-09-21 |
KR101824349B1 (ko) | 2018-01-31 |
EP3087614B1 (fr) | 2021-02-17 |
CN105849914A (zh) | 2016-08-10 |
CN105849914B (zh) | 2019-11-01 |
US20170301738A1 (en) | 2017-10-19 |
KR20160102265A (ko) | 2016-08-29 |
BR112016015034A2 (pt) | 2017-08-08 |
BR112016015034B1 (pt) | 2021-12-14 |
EP3087614A4 (fr) | 2017-02-08 |
JP6547273B2 (ja) | 2019-07-24 |
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